DE60112948T2 - POLYURETHANE DISPERSION IN ALCOHOL WATER SYSTEM - Google Patents

Abstract

A polyurethane dispersion and a method of making are provided. The polyurethane dispersion is stable in a mixture of alcohol and water. The dispersion comprises the reaction product of (a) an isocyanate terminated polyurethane prepolymer comprising the reaction product of (i) at least one oligomeric polyactive hydrogen compound insoluble in said alcohol, wherein said polyactive hydrogen compound is an alkyl, aryl, or aralkyl structure optionally substituted by N, O, and S; (ii) at least one polyisocyanate, and (iii) at least one polyactive hydrogen compound soluble in said mixture of alcohol and water; (b) a polyfunctional chain extender; and (c) a monofunctional chain terminator; wherein the equivalent ratio of difunctional chain extender to prepolymer isocyanate is 0.60 to 1.20.

Description

technical area

The The present invention relates to a cold seal adhesive composition in the form of a stable polyurethane dispersion in an alcohol-water system.

background

polyurethane is a generic term used to describe polymers is used by the reaction of a polyfunctional isocyanate with a polyfunctional alcohol to form urethane bonds getting produced. The term "polyurethane" has also been used in a more generic way to designate the reaction products of polyisocyanates with any polyhydric hydrogen compound used, included polyfunctional alcohols, amines and mercaptans. Polyurethanes are used in a variety of applications, including Elastomers, adhesives, coatings and impregnating agents.

For coating applications can Polyurethane polymers in water by incorporation of stabilizing Groups in their skeletons be dispersed. Anionic, cationic and nonionic dispersion stabilizing Groups have been used. Various aqueous polyurethane dispersions are made by experts in the field. For example, disclosed US Pat. No. 3,479,310 (Dieterich et al.) Water-dispersed polyurethane polymers, for themselves the use as waterproof coatings are suitable. The polymer is made of polyhydroxy compounds, polyisocyanates, optional chain extenders and a sufficient amount of a component with a group made of the ionic salt type. US-A-4,307,219 (Larson) discloses water-dispersible Polyurethane resin obtained by the reaction of hydrophilic diols, hydrophobic diols, diisocyanates and optionally chain extenders will be produced. Such a urethane resin can be used as protective coatings, primers and binders are used.

Even though aqueous Dispersions of polyurethanes have been widely disclosed, The inventors are no references to stable polyurethane dispersions in alcohol-water solvent systems, especially in the absence of hydrophilic stabilizing units, known. Stable polyurethane dispersions in hydroalcoholic (i.e. Alcohol-water systems are special for at least two reasons difficult.

First, the addition of lower alcohols (eg, C ₁ to C ₄ ) to water lowers the surface tension of the solvent system. For example, a 40 wt% ethanol-in-water system has a surface tension of about 31 dynes / cm as compared to a pure water system which has a surface tension of about 72 dynes / cm at about 20 ° C. A 60% by weight ethanol-in-water system has a surface tension of 27 dynes / cm at about 20 ° C. The reduction in surface tension may affect the ability to self-assemble hydrophilic and hydrophobic domains during dispersion preparation. Second, many of the polyurethane components (ie, starting reactants) are soluble in hydroalcohol solvent systems that result in solutions rather than dispersions. Polymer solutions have a much higher viscosity than polymer dispersions, which makes the solutions in certain operations, such as in the coating and spraying, difficult to process. Polymer solutions also tend to have a lower percentage of solids compared to polymer dispersions, making the former less attractive during coating operations and during shipment. Lower solids solutions also require longer drying times than dispersions, both because of the greater amount of solvent present and the higher affinity of the polymer for the solvent. In addition, the molecular weight of soluble polymers is often much lower than that of dispersions.

The U5-A 4,507,430 (Shimada et al.) Discloses a polyurethane emulsion water-based, which is a hydrogenated polyalkadiene polyol component and a polyisocyanate component. Shimada reveals that the materials as an adhesive or coating material for a polyolefin resin useful are applied and wet and by dry lamination, the heat and Pressure requires, dried or bonded or glued can. There was no disclosure of polyurethane dispersions in the hydro-alcohol solvent system.

The US-A Re. 34,730 (Salatin et al.) Discloses basecoat compositions formed from water which comprise (a) an anionic polyurethane resin comprising (i) a polyester resin component represented by the Re a component of a carboxylic acid _{component which} comprises at least 50% by weight of a long-chain C _18-60- acid and a polyol, and (ii) a mixture of at least one multifunctional compound having at least one active hydrogen functionality and at least one carboxylic acid functionality neutralized with an amine, (b) a polyisocyanate combined with a crosslinking agent; and (c) a rheology modifier. US-A-5,326,815 (Serdiuk et al.) Discloses a coating composition which comprises (a) an aqueous medium, (b) a water-dispersible polyurethane resin which is the reaction product of (i) a hydroxy-functional polyester resin component which is the reaction product of a carboxylic acid component which comprises at least two carboxylic acids, a C ₃₆ dimer fatty alcohol and a short chain polyol, (ii) a multifunctional compound having at least one active hydrogen group and at least one water stabilizing group, (iii) an active hydrogen containing cap or chain extender and (iv) a Polyisocyanate, and (c) an aminoplast crosslinking agent. The active hydrogen-containing capping agent is used in excess to terminate the isocyanate functional prepolymer to provide terminal hydroxyl groups for reaction with the crosslinking agent. Other patents which disclose the use of dimer fatty alcohols or polyesters derived from dimer acid in waterborne polyurethane dispersions for basecoat compositions include US Pat. No. 4,423,179 (Guagliardo), US Pat. No. 5,334,650 (Serdiuk et al.) And US Pat -A 5 370 910 (Hille et al.). None of the above references discloses a polyurethane dispersion in an alcohol-water system.

The US Pat. No. 5,672,653 (Frisch et al.) Discloses an anionic one of water formed polyurethane dispersion which is prepared by (a) Forming a prepolymer of hydroxy-terminated polybutadiene resin, an aliphatic isocyanate and an acid group containing diol; (b) neutralizing the acid; Disperse this in water; and (c) chain extension of the prepolymer with a diamine.

Cold seal properties of adhesives have been discussed by those skilled in the art. For example, US-A-5,616,400 (Zhang) discloses a dry-bink seal-coated sheet material consisting essentially of the reaction product of 50 to 80 percent polyester polyol, 15-25 percent aliphatic diisocyanate and 3 to 6 percent neutralized dimethylolpropionic acid base wherein the reaction product has a T _g between about -20 ° and 5 ° C. US 5 981 650 (Zhao et al.) Discloses an aqueous cold seal adhesive dispersion containing from 30% to 55% of a polyurethane ionomer having a T _{g of} between -50 ° C and 10 ° C which is the reaction product of a polyester polyol. and a polyether polyol mixture, an aliphatic diisocyanate and dimethylolpropionic acid with 0.05 to 4% colloidal amorphous silica reacted in situ with an organic NCO-containing moiety. The use of an alcohol-insoluble oligomeric diol is not disclosed in these patents nor the importance of regulating molecular weight through the use of chain terminators to obtain cold seal adhesive properties.

Water-soluble or water-dispersible polyurethanes have been disclosed for use in cosmetic formulations. The EP 656 021 B1 (Son et al.), WO 96/14049 (Emmerling et al.), U.S. Pat. No. 5,643,581 (Mougin et al.), U.S. Pat. No. 5,874,072 (Alwattari et al.), U.S. Pat. No. 5,972,354 (de la Poterie et al.), WO 99/43289 (Ohta et al.), EP 938 889 A2 (Son et al., And U.S. Patent No. 5,968,494 (Kukkala et al.) Are representative thereof, none of which use oligomeric, alcohol-insoluble, polyactive hydrogen compounds, such as oligomeric, alcohol-insoluble diols in the preparation of the polyurethane.

None the above explained Technologies recognizes the importance of regulating molecular weight through the use of chain terminators for obtaining cold seal adhesive properties, too Do not put the use of these materials in cosmetic or medical formulations.

requirement is polyurethane dispersions stable in alcohol-water solvent systems wherein the dispersion has one or more of the following properties possesses: ability to Formation of stable dispersions in hydro-alcohol systems, ability to form rapidly of films on skin or hair by simple evaporation at ambient conditions and ability to achieve a high solids content. In addition, show by drying down films formed of the dispersions have one or more of the following Properties: a high self-adhesion and yet low stickiness, low moisture sensitivity and high tensile strength.

Summary

The present invention provides a novel polyurethane-urea dispersion useful in counteracting a hydro-alcohol system can be prepared and dispersed in this. As used herein, the term "hydroalcohol" refers to C ₁ to C ₄ lower alcohol-based solvents mixed with water, wherein the weight ratio of lower alcohol to water is preferably at least 20:80, more preferably at least 40: 60, even more preferably at least 60:40, and most preferably at least 70:30 on a weight basis. The preferred lower alcohols include ethanol, 2-propanol and n-propanol. The term "hydro-alcohol" is synonymous with the term "alcohol-water".

As as used herein, "dispersion" generally means a two-phase system, in which a phase over contains a mass substance distributed individual particles, wherein the particles dispersed or inner phase and the mass substance is the continuous or outer phase is. In this invention, the continuous phase is the alcohol-water mixture and at least a portion of the polyurethane is in discrete particles. By "dispersion" is meant also that not necessarily the entire polyurethane polymer is alcohol-water-insoluble got to; Part of the polymer may be in the alcohol-water mixture soluble be. Dispersions are possible through the use of certain components in the solvent system insoluble are. It is desirable that the dispersion remains stable under ambient conditions. preferred Dispersions are at room temperature for more than 30 days, preferably more than 90 days, stronger preferably more than 180 days, and most preferably for more than Stable for 360 days.

According to one Aspect of the present invention is aware of the molecular weight of the polyurethane polymer limited to the production of a material, which in a coating forming on a substrate a high cohesive strength film, i. the adhesion the movie itself is high. In addition, many of these exhibit new formulations have a very low adhesion to other surfaces, such as Glass, up.

Short summarized, according to one Aspect, the invention provides a polyurethane dispersion which is stable in a mixture of alcohol and water, with the dispersion the reaction product of the following comprises: (a) an isocyanate-terminated one polyurethane, comprising the reaction product of (i) at least one polyactive Hydrogen compound that is insoluble in the alcohol, wherein the poly-active Hydrogen compound is an alkyl, aryl or aralkyl structure, which may be N, O or S or combinations thereof is substituted (referred to as "A" component for the sake of convenience); (ii) at least one polyisocyanate; and (iii) at least one polyactive hydrogen compound; which is soluble in the mixture of alcohol and water (simplicity half referred to as "B" component); (b) at least a polyfunctional chain extender; and (c) a chain terminator. According to one embodiment is the equivalent ratio of active hydrogen on the chain extender to the prepolymer isocyanate 0.6: 1 to 1.20: 1. According to a another embodiment the chain terminator is a monofunctional hydroxy or amine.

In a preferred embodiment is the polyurethane dispersion according to the invention stable in a mixture of alcohol and water and the dispersion includes the reaction product of (a) an isocyanate-terminated one Polyurethane prepolymer comprising the reaction product of (i) about 20 to 30 parts by weight hydrogenated polybutadiene diol, (ii) about 15 to 30 parts by weight of isophorone diisocyanate and (iii) about 0 to 10 parts by weight of sulfonated polyester diol and (iv) about 25 to 75 parts by weight of polytetramethylene oxide diol; (b) about 0.05 to 5 parts by weight ethylenediamine; and (c) about 0 to 5 parts by weight of 2-amino-2-methyl-1-propanol.

According to one more another embodiment is the polyurethane dispersion according to the invention useful as a cold seal adhesive. As used herein, the term "cold seal adhesive" (commonly referred to as "contact adhesive") means that the adhesive shows good self-adhesion properties and typically non-adherent or only very slightly adherent is chemically different surfaces at temperatures of about 15 ° to 50 ° C. If they are placed against each other, require cold seal adhesives typically a moderate pressure (as exerted by a fingertip pressure) to achieve a connection without the need of using greatly elevated temperatures. That is, a compound may be used at room temperature (i.e. about 20 ° to 30 ° C) and an even lower temperature (e.g., about 15 ° C) and at temperatures up to about 50 ° C be formed. Wärmehärtungs- or crosslinkers are typically not for the cold seal adhesive needed to form a connection.

As used herein, a material has "self-adherence" properties when it preferably adheres to itself or a chemically similar material under pressure or application of force without requiring greatly elevated temperatures (eg, without the need for temperatures above about 50%) ° C). Preferred compositions of the invention exhibit self-adhesion properties immediately after contact with themselves at room temperature (about 20 ° to 30 ° C). As used in the preceding sentence, means the term "immediate" is less than a few minutes, e.g. About 5 minutes, preferably less than 1 minute, more preferably less than 30 seconds, depending on the application.

A cold seal adhesive is to be distinguished from a pressure sensitive adhesive (PSA). A PSA typically has tack at room temperature, requires moderate pressure to achieve bonding (such as that applied by fingertip pressure), and adheres to a wide variety of substrates. A PSA is said to conventionally refer to an adhesive that exhibits permanent and aggressive tack to a wide variety of substrates after the application of moderate pressure. An accepted quantitative description of a PSA is given by the Dahlquist Criterion Guideline, which specifies that materials with a storage modulus (G ') of less than about 3 x 10 ⁵ Pascal (measured at 10 radians / second at a temperature of about 20 ° to 22 ° C) have PSA properties, while materials with a G 'exceeding this value do not have these properties.

The Polyurethane dispersions according to the invention are useful in a variety of applications where cold-sealing properties he wishes are. Close such applications the production of self-adhesive envelopes; at Food packaging applications where heat should be avoided (especially ice cream, sugar cubes, teabags, baked goods, Snacks, milk and Dairy products, dried and frozen food, Chocolates and other sweets, Meat, drinks, Spices / spice flavors, Sauces and pet food); when sealing cardboard boxes, bags and other containers; in bundle tapes; at the Bookbinding; for cigarette and detergent packaging; Liquid packaging; and twist envelopes, medical packaging articles, diaper closures and adhering to the skin medical articles.

One Advantage of the composition according to the invention is the use of an oligomeric, alcohol-insoluble polyactive hydrogen compound. Due to its hydrophobic nature, such a compound can be seen faster drying and improved hydrolytic stability over synthetic Cold seal adhesives of the prior art. Another advantage the composition of the invention is that she has adhesion similar to low-energy substrates provided by cold seal adhesives based on natural rubber but without the disadvantages associated with such adhesives. Close these disadvantages the discoloration, unpleasant odor, unwanted foam in wet form, hypersensitivity and the possibility anaphylactic shock due to the presence of natural latex proteins one.

Yet Another advantage of the composition according to the invention is that they have a low viscosity and rapid drying characteristics in addition to the unfolding of Has self-adhesive properties.

Consequently the composition is suitable for use as an impregnating agent in processes for the preparation of cohesive elastomeric bandages, as disclosed in US Pat. No. 4,699,133 (Schafer et al.); US Pat. No. 5,230,701 (Meyer et al.); US-A 5,692,937 (Zhang); and US Pat. No. 5,843,523 (Mazza et al.).

One Another advantage of the composition according to the invention is the ability to form hydrophobic films, making them useful in cosmetic applications usefulness obtained. Such applications require some degree of water resistance, transfer resistance or substantivity for skin, Nails or Hair. Close the applications z. As cosmetic makeup or cosmetic protective applications, such as Mascara, Primer, Rouge, Face Powder, Eyeliner, Eyeshadow, Insect repellent, nail polish, skin moisturizer, skin cream and body lotion, lipstick and sunscreen.

If the dispersion according to the invention in hair care products such as shampoos and conditioners and the like, The dispersion can be used for faster drying to care. It can also improve the moisture resistance of hairstyling agents improve when combined in small proportions with others Hair styling resins is used. The hair care products, as herein are not "remodeling" hair styling compositions. "Transformable" hairstyling composition means a composition that is restored or modified can be used without new material or heat being used. For example are for restoring or modifying the hairstyle in the case a "drooping" or festering loss (Zerzausen) no new materials, such as water or any form a fixative or heat required. The composition may be long lasting, such as 10 to 24 hours, resulting in a permanent styling effect.

In medical article applications, the skin may be treated with the polyuret of the invention Handispersion be coated and allowed to dry to form a film. A medical article which is also precoated with the dispersion of the present invention may be attached to the film. It is a significant advantage that the composition of the present invention can be adhered to the skin and need not be repeatedly removed in applications such as ostomy or bandaging wounds to prevent skin detachment. The adhesives prepared from the polyurethane dispersions of the present invention may also be used in any application in which self-sealing at ambient temperature is required.

Full Description of the invention

Short summarized, the dispersion is formed by forming the isocyanate-terminated Polyurethane prepolymer, chain extension of the prepolymer and chain termination of the prepolymer to obtain a polyurethane polymer which is stable and in one Alcohol-water solvent system is dispersed. Although it is currently preferred that to carry out the above steps one after the other, this is not necessary. The order of the steps can be changed and certain Steps can combined, such as chain extension and chain termination or prepolymer formation and chain termination etc. The steps and components that for their implementation are required are explained in detail below. When used will the dispersion typically on a substrate, such as a carrier material or a lining, coated, dried and hardened to Formation of a movie.

As As used herein, the term "isocyanate-terminated polyurethane prepolymer" (alternately referred to as "isocyanate-functional Polyurethane prepolymer ") Reaction product of at least one polyisocyanate and at least a polyactive hydrogen compound (i.e., polyol). In general the reaction is carried out with a molar excess of isocyanate groups to form an oligomer, which is urethane, urea, thiourethane-functional Groups and combinations thereof may have. The prepolymer can be in an equivalent ratio of Isocyanate groups to active hydrogen reactive groups of higher than 1.6, preferably higher being 1.8, and most preferably about 2.0 or higher become.

As used herein a "polyol" compounds, which active hydrogen according to the Zerevitanov test C. R. Noller, Chemistry of Organic Compounds, Chapter 6, pages 121-22 (1957) is described. The term "polyol" means next a connection with an average functionality higher than 1, preferably higher than 1.8, and most preferably about 2.0 or higher, but less than about 6, preferably less than about 4, and most preferably about 3 or less. This should include compounds which (i) alcohol groups on primary, secondary and tertiary Have carbon atoms, (ii) primary and secondary amines, (iii) mercaptans and (iv) mixtures of these functional groups. As a result, can the polyurethane dispersions of the invention Urea bonds, z. B. from the reaction of isocyanate-functional Polyurethanes with amines, which polymers are more conveniently referred to as "polyurethane ureas". Polyols useful for making the prepolymer have a molecular weight from 62 to 10,000, preferably from 200 to 5,000 and most preferably from 400 to 3000.

The "A" component is preferably in concentrations of at least 5%, preferably at least 10%, and most preferably at least 20% by weight, based on the total weight the "A" component, the Polyisocyanate and the "B" component, before. The latter Two components are explained in detail below. The "A" component is in the alcohol of the alcohol-water mixture insoluble, which is used to form the dispersion. The term "insoluble" generally means that At least 1 gram of the compound is not soluble in about 4 grams of alcohol at about 25 ° C. Certain polyols can a warming require to melt to determine if they are under application of this characterization method are insoluble.

The Polyols for the use as "A" component suitable have an alkyl, aryl or aralkyl structure, optionally by N, O, S and combinations thereof in and / or on the chain is substituted. The "A" component has one number average molecular weight of preferably above about 300, stronger preferably from above about 400, and most preferably from above about 500, but preferably less than about 10,000, more preferably less than about 5000, and most preferably less than about 3000.

Monomeric polyols, such as the C ₃₆ dimer fatty alcohol available as PRIPOL 2033 from Uniquema North America, Chicago, IL, may be used. Oligomeric polyols with an average of about 1.6 to about 4 hydroxyl or amino groups are preferred. One type of preferred oligomeric polyol useful as the "A" component is aliphatic polyester polyol based on diacids and / or diols having more than 10 carbon atoms and preferably more than 20 carbon atoms. Commercially preferred polyester polyols are PRIPLAST 3191, 3192, 3196, 3197, 1906 and 1907 from Uniquema North America, Chicago, IL, USA, based on a 36-carbon diacid and / or a diol. Specific ingredients used in the preparation of these diols are the following: for PRIPLAST 3192 - dimer acid, adipic acid and 1,6-hexanediol; for PRIPLAST 3193 - dimer acid and ethylene glycol; for PRIPLAST 3194 - dimer acid, adipic acid and ethylene glycol; for PRIPLAST 3196 - dimer acid and 1,6-hexanediol; for PRIPLAST 3197 - dimer acid and dimerdiol; for PRIPLAST 1906 - isophthalic acid and dimerdiol; and for PRIPLAST 1907 - terephthalic acid and dimerdiol. The term "dimer acid" is understood to be a _C36 diacid formed by dimerization of unsaturated C ₁₈ fatty acids. The term "dimer diol" is understood to be a di-C ₃₆ polyol formed by hydrogenation of the _C36 dimer acid. Another preferred oligomeric polyol are hydroxy-terminated polyalkadienes including polybutadienes and polyisoprenes. A commercially preferred hydroxy-terminated polybutadiene is POLY bd resin from Elf Atochem North America, Philadelphia, PA.

Yet another preferred oligomeric polyol are hydrogenated polyalkadiene polyols, including hydrogenated Polyisoprene and hydrogenated polybutadiene, the latter not less as a 19 wt% 1,2-butadiene addition product having. Commercially preferred hydrogenated polybutadiene diols include KRATON L2203 from Shell Chemical, Houston, TX, and POLYTAIL resins from Mitsubishi Chemical, Tokyo, Japan. A preferred type of oligomeric polyamine are amine-terminated butadiene polymers and butadiene-acrylonitrile copolymers. A commercially preferred amine is HYCAR ATBN from B.F. Goodrich, Cleveland, OH, USA.

silicone polyols and perfluoroalkyl-functional polyols should in case of their use preferably not more than about 5% by weight of the total composition present, as would be expected that their low surface energy properties the desired adhesion characteristics based on the teachings of US-A 5,679,754 (Larson et al.).

In addition to alcohol-insoluble Polyols can be "monomeric" polyols with a low molecular weight can be used to form the prepolymer. examples for the monomeric polyols include ethylene glycol, Propylene glycol, butylene glycol, hexamethylene glycol, diethylene glycol, 1,1,1-trimethylolpropane, pentaerythritol, aminoethanol and the like one. In case of their use should be the amount of monomeric polyols preferably kept low to the viscosity of the prepolymer to minimize.

The amounts of polyol and isocyanate used to form the prepolymer interfere with the physical and chemical properties of the final polymer. Properties that can be varied include, but are not limited to, ductility, water absorption, tensile strength, modulus, abrasion resistance, minimum film-forming temperature, glass transition temperature, UV light resistance, and resistance to hydrolysis and color stability. In general, longer chain polyols tend to provide films formed from the dispersions that are more ductile and have lower _Tg , higher elongation, and lower tensile strength. In contrast, shorter chain polyols tend to provide films that have high modulus, higher tensile strength, and higher T _g . Aliphatic polyols tend to provide materials with reduced water uptake, whereas diols containing heteroatoms in the backbone (e.g., polyether polyols) tend to have increased water uptake. The amount of water remaining in the film can affect its tensile and elongation properties. When resistance to hydrolysis is important, polyols should be chosen which are hydrolytically stable, such as polyether and polysiloxane polyols, and polyolefin based backbone polyols. Polyester polyols can be used which are hydrolytically stable, such as those based on hydrophobic subunits (PRIPLAST polyols from Uniquema), those based on isophthalic acid, and polycaprolactone polyols.

Representative polyisocyanates that can be used to form the isocyanate-functional poly-urethane include aliphatic and aromatic polyisocyanates. Suitable polyisocyanates are preferably aliphatic or cycloaliphatic isocyanates. The aromatic isocyanates are less preferred because they tend to discolor in UV light, making them undesirable in outdoor applications. Particularly preferred diisocyanates include dicyclohexylmethane-4,4'-diisocyanate (often referred to as H ₁₂ MDI) and 3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane (often referred to as isophorone diisocyanate or IPDI), both from Bayer Corp. , Pittsburgh, PA, USA, under the trade designations DESMODUR W and DESMODUR I, respectively. Other preferred diisocyanates include (i) tetramethylene diisocyanate, (ii) 1,3-bis (isocyanatomethyl) cyclohexane, (iii) 1,3-bis (1-isocyanato-1-methylethyl) benzene, (iv) di phenylmethane-4,4'-diisocyanate (often referred to as MDI), (v) 4,4'-4 "-triisocyanatotriphenylmethane, (vi) polymethylene polyphenylene polyisocyanate (often referred to as polymeric MDI), (vii) toluene diisocyanate (commonly referred to as TDI), (viii) hexamethylene diisocyanate (often referred to as HDI), (ix) dodecamethylene diisocyanate and (x) m- and p-xylene diisocyanate.

Other useful Close polyisocyanates those disclosed in US-A 3,700,643 (Smith et al.) and US-A 3,600,359 (Miranda) are described. Mixtures of polyisocyanates can also such as ISONATE 2143L, available from Dow Chemical Co., Midland, MI, United States.

The Polyurethane prepolymer is alcohol-water-dispersible made by using a "B" component with at least an alcoholic-water-soluble polyactive hydrogen compound. That is, the "B" component serves primarily the Stabilization of the polyurethane dispersion in a water or alcohol-water solvent system. The term "alcohol-water-soluble" generally means That at least 1 gram of the compound in about 4 grams of an alcohol-water mixture at about 25 ° C soluble is. Certain connections can heating to melt to determine if they are soluble using this characterization method. The in this Characterization method used alcohol-water mixture should the same alcohol-water mixture used to prepare the hydro-alcohol dispersing medium is used. The alcohol-water solubility This compound is characterized by the presence of an ionic group, a residue capable of forming an ionic group, or a polyester, polyether or polycarbonate group having a Proportion of 5 or less, preferably 4 or less of carbon atoms for each Oxygen atom and mixtures thereof.

When present, the ionic group of the "B" component can be anionic, cationic or zwitterionic. The cationic groups may be derived from the isocyanate or polyol component, but are most conveniently added as a polyol component. The cationic group can be introduced directly into the prepolymer. For example, a quaternary diol, such as VARIQUAT 1215, can be directly reacted into the prepolymer. Alternatively, a precursor group may be converted to the prepolymer and thereafter rendered cationic in a subsequent reaction. For example, active hydrogen-functional tertiary amines such as methyldiethanolamine and its polyethoxylated adducts can be incorporated into the prepolymer backbone and then protonated with a mineral or organic acid to form an ionic salt or alkylated to form a quaternary ammonium group. The reaction of the incorporated tertiary amine with hydrogen peroxide, propanesultone or lactone gives zwitterionic radicals. Preferred stabilizing cationic components are very water-soluble, generally have a solubility in water of at least 1% by weight and preferably more than 10% by weight. Preferred stabilizing cationic compounds have the following structure: RN ⁺ (R ₂ ) [(CH ₂ CH ₂ O) _n H] ₂ X ^- wherein R is C ₁ to C ₁₈ alkyl or C ₆ to C ₁₈ aryl or aralkyl optionally substituted in and / or on the chain by N, O, S and combinations thereof;
R _{2 is} hydrogen or C ₁ to C ₁₈ alkyl;
n is an integer of about 1 to 200, preferably 1 to 50, and most preferably 1 to 20; and
X is halogen, sulfate, methosulfate, ethosulfate, acetate, carbonate or phosphate.

preferred cationic stabilizing compounds include protonated and alkylated Methyldiethanolamine and PEG 2-cocomonium chloride and PEG-15 cocomonium chloride, available by CK Witco, Greenwich, CT, USA, as VARIQUAT 638 and VARIQUAT, respectively K1215, a.

It is possible, to introduce cationic compounds that are a single reactive Have hydrogen group. However, they are less preferred.

worin jedes R₁ unabhängig eine zweiwertige aliphatische Gruppe mit einem durchschnittlichen Molekulargewicht von 200 bis 600 ist, umfassend Ether- oder Esterfunktionelle Gruppen, gewählt aus der Gruppe bestehend aus Poly(C₂- bis C₄-Alkylenoxid), vorzugsweise:
-CH₂-CH₂(OCH₂-CH₂-)_n
-C(CH₃)H-CH₂-(OC(CH₃)H-CH₂-)_n-,
-(CH₂)₄-(O(CH₂)₄)_n-,
-(CH₂)_m-CO-[-O-(CH₂)_m-CO-]_n-Gruppen und Mischungen davon,
worin m eine ganze Zahl von etwa 2 bis 5 ist und n eine ganze Zahl von etwa 2 bis 15 ist und M ein Kation ist, vorzugsweise M Na ist, doch M H, K, Li oder ein primäres, sekundäres, tertiäres oder quaternäres Ammoniumkation, wie Ammonium-, Methylammonium-, Butylammonium-, Diethylammonium-, Triethylammonium-, Tetraethylammonium- und Benzyltrimethylammoniumkation sein kann.The anionic stabilizer used in the present invention may be either the isocyanate component or the polyol component. Typically, and most conveniently, the anionic stabilizer is present as a polyol component. The anionic group can be sulfonate, phosphonate, phosphate and carboxylate, but is preferably either sulfonate or carboxylate and most preferably a sulfonate. The most preferred sulfonates are the sulfonated polyols described in US-A 4,738,992 (Larson et al.). Particularly preferred sulfonates are polyester diols of the following structure:

wherein each R _{1 is} independently a divalent aliphatic group having an average molecular weight of 200 to 600 comprising ether or ester functional groups selected from the group consisting of poly (C ₂ to C ₄ alkylene oxide), preferably:
-CH ₂ -CH ₂ (OCH ₂ -CH ₂ -) _n
-C (CH ₃₎ H-CH ₂ - (OC (CH ₃₎ H-CH ₂ -) _n -,
- (CH ₂ ) ₄ - (O (CH ₂ ) ₄ ) _n -,
- (CH ₂ ) _m -CO - [- O- (CH ₂ ) _m -CO-] _n groups and mixtures thereof,
wherein m is an integer from about 2 to 5 and n is an integer from about 2 to 15 and M is a cation, preferably M is Na, but MH, K, Li or a primary, secondary, tertiary or quaternary ammonium cation, such as ammonium, methylammonium, butylammonium, diethylammonium, triethylammonium, tetraethylammonium and Benzyltrimethylammoniumkation can be.

suitable Carboxylate and carboxylic acid functional Close polyols dimethylolpropionic and their polyethoxylated derivatives and acid-grafted polyethers, such as the UCARMOD polyols available from Union Carbide Specialty Chemicals Div., Danbury, CT, USA. these can with an organic or inorganic base either before or after the preparation of the prepolymer be neutralized.

Around Alcohol-water or water dispersibility should be achieved the ionic equivalent weight of the prepolymer (Grams of prepolymer per equivalent ionic functionality) in the range of 1000 to 15,000, preferably 1500 to 12,500, more preferably 2000 to 10,000, most preferably 2500 to 7500.

Examples for oligomers Polyols which have sufficiently polar nonionic groups, such as ether or ester functionality, which accounts for 5 or less carbon atoms for each Oxygen atom to provide alcohol-water solubility, include (i) Polyoxyalkylenediols, -triols and -tetrols, (ii) polyoxyalkylenediamines and triamines, (iii) polyester diols, triols and tetrols of organic polycarboxylic and polyhydric alcohols and (iv) polylactone diols, triols and tetrols having a molecular weight of from 106 to about 2000. preferred oligomeric polyols and polyamines include (i) polyethylene oxide homopolymers (e.g., CARBOWAX series from Union Carbide, Danbury, CT, USA), block copolymers of ethylene oxide and propylene oxide (e.g., PLURONIC surfactants from BASF Corporation, Mount Olive, NJ, USA), random copolymers of ethylene oxide and propylene oxide (e.g., UCON FLUIDS of Union Carbide, Danbury, CT, USA), silicone copolyols and surfactants based on polyethylene oxide, as in US-A 4,667 661 (Scholz et al.), (Ii) polyoxypropylene diols and triols, such as the ACCLAIM series of polyols from Arco Chemical, Newtown Square, PA, USA, (iii) Polyether diamines and triamines, such as the JEFFAMINE series, available from Huntsman Corporation, Salt Lake City, UT, USA, (iv) polyether polyols, like the TERATHANE series (which is a polyoxytetramethylenediol), available from E.I. duPont Co., Wilmington, DE, USA, and the POLYMEG series, available from Quaker Oats Co., Chicago, Ill., USA), (v) polyester polyols, such as MULTRON, which is a poly (ethylene adipate) polyol available from Bayer Corporation, Pittsburgh, PA, USA), (vi) polycarbonate diols such as those described by Steel USA Co., Peabody, MA, USA, and (vii) polycaprolactone polyols, like the TONE series, available from Union Carbide, Danbury, CT, USA. Polythioetherpolyole are also useful.

The Reaction of the above explained Components (i.e., the "A" component, the Polyisocyanate and the "B" component) to form the prepolymer depends on their selection. Aromatic isocyanates are generally much more reactive as aliphatic isocyanates and can be reacted with polyols be without heat is required because the reaction is exothermic. The reaction can be considered 100% solids (i.e., little to no solvent) take place or may be in an optionally polar organic solvent, which is not reactive with the isocyanate be performed. Such solvents shut down for example, acetone, methyl ethyl ketone (MEK), methoxypropanol acetate (PM acetate), dimethylacetamide, tetrahydrofuran, N-methylpyrrolidinone and mixtures thereof. Preferably, the used solvent not the removal in the final composition. It is also possible solvent and / or softening agents incorporated in the prepolymer stay behind which become part of the final dispersion.

at a use of preferred aliphatic isocyanates with polyfunctional Alcohols are high solids concentrations and elevated reaction temperatures from about 50 ° C to 80 ° C desired, so that high conversions of monomers to polymer in a reasonable Time can be done z. In less than eight hours, preferably less than three Hours. Preferred embodiments, in the isophorone diisocyanate or hexamethylene diisocyanate and aliphatic primary or secondary Alcohols are incorporated, usually about 2 hours long at about 80 ° C heated in the presence of a small amount of catalyst.

helpful Close catalysts Salts such as dibutyltin dilaurate and dibutyltin diacatet, and amines such as Triethylamine, DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) and DABCO (1,4-diazabicyclo [2.2.2] octane) in useful Concentrations of about 0.01 to 1.0 mol% (based on the isocyanate reagent) one. Preferred catalysts are not irritating to the skin and are not skin-sensitizing. The most preferred catalysts are those that and Polymer backbone can be tied and therefore not herauslösbar such as FASTCAT 4224 from Elf Atochem North America, Philadelphia, PA, USA, and certain alcohol and amine functional tertiary amine catalysts, such as methyldiethanolamine and tetramethylguanidine. For batchwise preparations From about 100 to 1000 grams, we usually used about 0.1 gram FASTCAT 4224 per 100 grams of total resin.

The relationship from polyisocyanate to polyol is adjusted so that the prepolymer has a molecular weight of about 1000 to 25,000. The equivalents of polyisocyanate preferably the total equivalents of polyol (i.e., the total equivalents active hydrogen), with the equivalent excess preferably about 1.1: 1 to 6: 1, stronger preferably about 1.5: 1 to 3: 1, and most preferably about 1.8: 1 to 2.2: 1.

To the formation of the prepolymer the molecular weight should be increased to give a composition with the desired properties. This step is accomplished by reacting the prepolymer with a "chain extender". As used herein, the term "chain extender" means a polyhydric hydrogen compound with a functionality from about 2 to 4, stronger preferably 2 to 3, and most preferably about 2 and generally having a molecular weight of about 30 to 2000, preferably 30 to 1000. Preferred chain extenders are polyfunctional alcohols, amines or carboxylic acid hydrazides. Most preferred chain extender are polyfunctional amines and carboxylic acid hydrazides.

helpful Close polyamines the following: ethylenediamine; 1,6-diaminohexane; piperazine; Tris (2-aminoethyl) amine; and amine-terminated polyethers such as JEFFAMINE D230 and JEFFAMINE D400 from Huntsman Corporation, Salt Lake City, UT, USA.

helpful carboxylic acid hydrazides shut down adipic and oxalic dihydrazide one. Especially useful Polyfunctional alcohols include alkylene diols having 2 to 24 carbon atoms, such as ethylene glycol; 1,4-butanediol; and 1,8-octanediol, one. helpful Close polythiols 1,2-ethanedithiol; 1,4-butanedithiol; 2,2'-oxytris (ethane thiol) and di- and tri-mercaptopropionate esters of poly (oxyethylene) diols and triols. Water is as well useful as a chain extender, because it reacts with isocyanate to form an unstable carbamic acid Carbon dioxide loses react, releasing an amine. This Amin is then for the reaction with another isocyanate available.

If the prepolymer a functionality of 2 or less and the chain extender is difunctional, the ratio of Isocyanate to active hydrogen in the chain extension step preferably about 0.6: 1 to 1.2: 1, more preferably 0.75: 1 to 1: 1, and most preferably from 0.80: 1 to 1: 1 (except when Water as the only chain extender in which case, water is in a large molar excess may be present). When the prepolymer a functionality from higher as 2 possesses due to the use of polyols or polyisocyanates with a functionality from higher than 2, the ratio should be from isocyanate to the active present in the chain extender Hydrogen proportional down to a set To prevent gelation and the molecular weight of the formed Polyurethane polymer in a suitable range to maintain cold seal performance provided. Furthermore, if the prepolymer has a functionality of 2 or less, uses a chain extender with a slightly higher functionality be, for. As a minor amount of trifunctional amine.

The dispersions of the present invention are in water or alcohol-water, with relatively high concentrations of a lower alcohol (typically greater than 20:80 w / w alcohol to water). In this environment, endcapping of the isocyanate-functional prepolymer can occur when the isocya nat reacts with the alcohol solvent. Therefore, the use of a polyfunctional amine as a chain extender is preferred because amines are much more reactive toward isocyanate than the lower alcohol, thus achieving better molecular weight regulation. For use in skin and hair contact applications where irritation and / or sensitization is a concern, the most preferred ratio of isocyanic equivalents to amine equivalents is about 1: 0.60 to 1: 0.99 to ensure that little to no residual free amine remains in the final dispersion.

The solvent used as the dispersing medium is selected from the group consisting of a lower alcohol (branched or straight aliphatic C ₁ to C ₄ alcohol), water and mixtures thereof. The preferred lower alcohols are ethanol, n-propanol and 2-propanol (IPA). The most preferred solvents are water, IPA, ethanol and mixtures thereof. Preferably, the alcohol to water ratio is from 20:80 to 90:10 w / w, and more preferably, the ratio is from 70:30 to 85:15. Generally, higher amounts of alcohol result in a dispersion having faster drying times.

The solvent system may also include additional solvents. For example, other rapidly evaporating solvents may be used, such as hexamethyldisiloxane (HMDS); cyclic silicones (D ₄ and D ₅ ); C ₄ -C ₁₀ alkanes including isoparaffins such as Permethyl 97A and Isopar C; Acetone; Hydrofluoroethers (HFEs) and the like. Certain HFEs, such as HFE 7100, have the added benefit of certain applications. When added to the hydroalcohol mixtures at levels above about 15-25% by weight, the composition becomes non-flammable.

In an embodiment For example, the reaction that forms the polyurethane polymer can be accomplished by the Use of chain termination species. These Species stop the growing polymer chain, reducing the molecular weight and the physical properties of the polymer are regulated. In one embodiment becomes a diamine chain extender in excess used. The excess diamine acts as a chain terminator. Another useful chain terminator is 2-amino-2-methyl-1-propanol (AMP), which is approximately 0.1 to 2.0 parts based on the total weight the polyurethane polymer is used. Monofunctional amines or Alcohols are useful as chain terminators. An example of one preferred monofunctional alcohol is ethanol, which is further than a part of the dispersing medium can act. The chain termination can while the prepolymer formation before or after chain extension or before or after dispersion in a solvent mixture. In the present preferred process, an amine chain terminator with the chain extender mixed and the solvent before the addition of the prepolymer added.

manufacturing the dispersion

The Dispersions of the present invention can be prepared in a variety of methods getting produced. In a first method, the prepolymer the solvent as 100% solids are added or first with another solvent dilute be that later can be removed or not. When the solvent is removed This is preferably more volatile as either water or the lower alcohol. In another Process can be the prepolymer in one part or in the whole solvent mixture or in a proportion of the solvent mixture under subsequent Adding extra solvent be dispersed. Any additional solvent after dispersion added is added slowly, preferably to ensure that the dispersion their stability maintains. In yet another method, the prepolymer and / or the dispersion solvent heated or cooled become. In yet another method, the prepolymer in the solvent before, simultaneously with or after the chain extension are dispersed, and there was a chain extension to the solvent mixture added.

The preferred dispersion method involves heating the prepolymer to temperatures of about 45 ° C up to 80 ° C, by its viscosity to reduce. The heated prepolymer gets into a fast-moving, high shear mixing device, such as a homogenizer, which the solvent contains given. Thereafter, the amine, a chain extender, in a predetermined Rate added. Alternatively, the amine may be for certain formulations the solvent mixture can be added first and the heated prepolymer can be fast mixing solvent mixture be added.

For an alcohol-water system, the proportion of lower alcohol is preferably at least 20% by weight, more preferably at least 40% by weight, even more preferably at least 60% by weight, and most preferably at least 70% by weight. , The proportion of lower alcohol is preferably not more than 90 %, and more preferably not more than 85%. As used herein, "percent solids" is defined as the percentage of nonvolatile components present in the dispersion. For cold seal applications in which a uniform continuous coating of 10 to 50 microns is desired, the percent solids should be greater than about 15 weight percent, preferably greater than about 25 weight percent, and most preferably greater than about 40 weight percent. -%. For other applications where a lighter or a discontinuous coating is desired, percent solids may be used down to 2% and less advantageously.

According to one Aspect of the present invention may be films of the dispersion are produced, which has a very low adhesion or stickiness on most surfaces, like skin, hair and glass, but a comparatively high self-adhesion exhibit. In a test using the methods described herein is the relationship self-adhesion to the adhesion on glass larger than about 2: 1, preferably greater than about 3: 1, stronger preferably greater than about 5: 1, and most preferably, greater than about 10: 1 embodiments is the relationship greater than 20: 1 and even 30: 1, although such high ratios probably not for all applications required are. When used in cold seal applications (which requires very low tack, but high self-adhesion) is the adhesion preferably less than about 10 Newton per decimeter (N / dm) of glass, stronger preferably less than about 8 N / dm, and most preferably less as about 5 N / dm while the self-adhesion higher than about 10 N / dm, preferably higher than about 20 N / dm, stronger preferably higher is about 25 N / dm and most preferably higher than about 30 N / dm.

We found that a prerequisite for the production of strong self-adhesive coatings the molecular weight of the polyurethane in the final dispersion. The preferred average Molecular weight is about 5,000 to 50,000, stronger preferably about 15,000 to 35,000, and most preferably about 20,000 to 30,000. If the molecular weight is too high, has the resulting adhesive has a very low self-adhesion. If the molecular weight is too low, the adhesive tends to a higher one Stickiness or adhesion to other substrates.

The Molecular weight of the polymer in the final dispersion can be regulated in several ways. The first method concerns the alcohol-to-water ratio, the is used as a dispersing medium. We found that for certain Polymers self-adhesion in alcohol-to-water ratios greater than about 75:25 w / w, preferably above 80: 20, and stronger preferably at or above about 85:15 can be achieved. Without to be bound to a theory, one assumes that at higher Alcohol-to-water ratios more of the isocyanate with the monofunctional alcohol solvent reacts, which limits the molecular weight. It will too assumed that the higher alcohol conditions to a better solution and resolution of the prepolymer to lead, which also reduces the likelihood of reaction of the isocyanate groups is increased with the monofunctional lower alcohol solvent.

The Molecular weight of the prepolymer may also be due to the type of alcohol used as the solvent be regulated. primary Alcohols can to a higher one Self-adhesion as a secondary Alcohol solvent as isopropanol lead.

The Molecular weight of the prepolymer can continue through the dispersion method and the method of Addition of the chain extender be regulated. Currently Let's assume that dispersing the prepolymer in the solvent first, followed by an amine addition (as a chain extender) in slower rates also improve the degree of self-adhesion can. However, a slow amine addition rate can reduce the degree of stickiness increase.

The presently preferred method of regulating the degree of self-adhesion is to use monofunctional amines to be added before or during the chain extension step. This process results in end-capping of some isocyanate groups, limiting the molecular weight. The monofunctional amines generally have the following structure: R ₁ R ₂ NH wherein R ₁ and R _{2 are} independently H or C ₁ to C ₂₂ alkyl; C ₆ - to C ₂₈ -aryl or C ₆ - to C ₂₈ aralkyl optionally substituted in available positions by N, O and S, including alcohol tertiary amine, quaternary amine, ketone, and carboxylic acid substitutions. Preferred monofunctional amines are those which would cause little skin irritation if left unreacted in the formulation, such as 2-amino-2-methylpropanol or primary and secondary amines of higher alkyl, as well as primary and secondary alkanolamines.

Of the Proportion of ionic stabilizer can also cause self-adhesion. Currently, it is assumed that higher Shares of stabilizer can lead to lower self-adhesion.

The Formulations of the present invention may also include softening agents containing either the prepolymer can be added directly or the solvent mixture can be added. The use of softening agents may prevent the use of allow less solvent and thus produce faster drying films. Where softening Should be used, the base prepolymer should be formulated, to ensure that the plasticized adhesive has sufficient Has tensile strength. this could the use of lower molecular weight polyols (prepolymers with a lower NCO equivalent weight) require. Preferred emollients are cosmetically acceptable Emollients, such as those described in US Pat. No. 5,951,993, column 17, Line 35 to column 21, line 6, are described.

Other compounds may be added to enhance or to obtain specific properties, provided that they do not interfere with coating and filming properties. The dispersion may contain defoaming agent. Particularly useful defoaming agents include, for. Surfynol ^™ DF 110L (a high molecular weight acetylenic nonionic glycol surfactant available from Air Products & Chemicals, Inc.), SWS-211 (a silicone additive available from Wacker Silicone Corp.), Dehydran ^™ 1.620 (a modified polyol / polysiloxane adduct available from Henkel Corp.), Additive 65 (a silicone additive available from Dow Corning).

The dispersion may also include flow and leveling agents such as Igepal ^™ CO-630 (an ethoxylated nonionic nonylphenol surfactant available from Rhone-Poulenc Surfactant & Specialty Div.), FLUORAD FC-171 (a nonionic surfactant available from 3M Company), FLUORAD FC -430 (a nonionic surfactant, available from 3M Company) and Rexol ^™ 25/9 (a nonionic alkylphenol ethoxylate surfactant, available from Hart Chemical Ltd.). Optionally, the dispersion may contain rheology modifiers, such as the Acrysol ^™ RM-825 association thickeners, Acrysol TT-935, all available from Rohm and Haas Company.

In order to increase the life of the coatings produced from these dispersions, especially in outdoor applications, photostabilizers may be added. Useful photostabilizers include Tinuvin ^™ 400 (a hindered amine light stabilizer), Tinuvin ^™ 292 (a hindered amine light stabilizer), both commercially available from Ciba-Geigy Ltd. Also, antioxidants such as IRGANOX 245, available from Ciba-Geigy Ltd., and Naugard 445, a 4,4'-bis (α, α-dimethylbenzyl) diphenylamine available from Uniroyl Chemicals may be added. For applications subject to ultraviolet light (UV) degradation, at least about 0.1 parts by weight of the UV light stabilizer per 100 parts by weight of polyurethane dispersion may be used to inhibit and retard yellowing and photodegradation , Typically, about 0.1 to 10 parts, preferably about 1 to about 10 parts per 100 parts of the polyurethane dispersion is used.

Examples

The explain the following examples Various specific features, advantages and other details of the invention. The specific materials specified in these examples and Quantities as well as other conditions and details should not be in one Be made way, whereby the scope of this invention inappropriate limited would. The percentages are by weight unless otherwise specific is specified.

test method

The Tackiness of the adhesives of the invention was qualitatively evaluated by a "finger-response" test, which a light touch and short contact time, and it became a value of 1 to 5, where 1 = no sticking; 1.25 = very, very little stickiness, 1.5 = very low tack, 2 = little tack, 2.5 = low to medium stickiness, 3 = medium stickiness, 3.5 = medium to high tack, 4 = high tack and 5 = very high tack mean. On this scale has the transparent tape SCOTCH MAGIC of Minnesota Mining and Manufacturing Co. (3M), St. Paul, MN, USA, a rating of 5.

A 180 ° -Ablöse-adhesion is a measure of the power for removing an adhesive-coated, flexible surface material from a substrate after a specified residence time and at a specific angle and a specific removal rate is required. It became according to the directive test PSTC # 1 for pressure sensitive bands (Pressure-Sensitive Tape Council test PSCT # 1). In our Tests is the surface material a 0.0015 inch (38 micron) polyester film, which is residence time 1 minute (unless otherwise stated), and the train rate was 12 inches (30.5 cm) per minute. For adhesion to glass is a ½ inch (1.3 cm) × 6 Inch (15 cm) tall Tape strips on a fresh with methyl ethyl ketone cleaned Placed glass plate. The glass plate is placed on the platform of a I-mass peel tester attached by Instrumentors, Inc., Strongsville, OH, USA. The stripe is applied to the substrate by rolling twice (once in each Opposite direction) with a 4.5 lb (2 kg) rubber roller. To one (1) minute of dwell time, one end of the tape is knocked back until it almost touches itself, making an angle of 180 ° with the glass plate is formed and clamped in the jaws of the I-mass tester. The average force used to cut off the adhesive-coated Tape required by the glass plate is called the adhesion Glass recorded. This measurement of force is in ounce units obtained per half inch and in Newtons per decimeter (N / dm) Multiply converted by the conversion factor 2.189.

The self-adhesion a sample is performed by modifying the PSTC # 1 standard test Laminating the ½ inch x 6 inches huge Tape to the adhesive coated side of a ¾ inch strip (1.9 cm) × 8 Inch (20 cm) of the same tape with two coats measured with the 2 kg rubber roller. After one (1) minute of residence becomes the ¾ inch band to the platform of the I-mass peel tester adhered with a double coated 3M SCOTCH tape and the ½ inch tape is detached from it at an angle of 180 °.

manufacturing the sulfopolyester diol precursor Sulfopolyester diol A

A Mixture of dimethyl 5-sodium sulfoisophthalate (DMSSIP, 337.3 g, 1.14 mol, from E.I. DuPont de Nemours, Wilmington, DE, USA), diethylene glycol (DEG, 424g, 3.99 moles) from Aldrich Chemical Co., Milwaukee, WI, USA) and zinc acetate (0.82 g, ex Aldrich) was heated to about 180 ° C and the methanol by-product was distilled off from the reaction mixture. After 4.5 hours, NMR analysis of the reaction product showed that less than about 1% of residual methyl ester in the reaction product was present.

Dibutyltin dilaurate catalyst (1.51 g, 2.4 mmol, from Alfa Chemical Co., Ward Hill, MA, USA) was added to the The above reaction product was added, the temperature was at about 180 ° C held, and ε-caprolactone (650 g, 5.7 mol, from Aldrich) was added portionwise over a Period of 30 minutes added. When the encore was finished, became the reaction mixture kept at about 180 ° C for 4 hours. The product is designated as sulfopolyester diol A.

The Determination of hydroxyl equivalent weight the reaction product was as follows. A 5.12 g sample of Product mixture was dissolved in 20 ml of methyl ethyl ketone (MEK). Isophorone isocyanate (3,13 g, 14.1 mmol, from Aldrich) and dibutyltin dilaurate (0.02 g) added. The solution was heated at about 80 ° C for about 4 hours. The solution was at room temperature cooled. A solution of dibutylamine (4 milliliters (mL) of a 1.72 molar solution in MEK) was added and the solution became 15 minutes long stirred. Thereafter, 20 ml of methanol and 4 to 5 drops of bromophenol blue indicator added, and the solution was charged with 2.17 ml of a 1.0 molar hydrochloric acid solution in Titrate water to a yellow endpoint. This corresponds to one Hydroxyl equivalent weight of about 218 (theoretical hydroxyl equivalent weight for sulfopolyester diol A is 235).

sulfopolyester B

A reactor equipped with a mechanical stirrer, nitrogen purge, and a distillation apparatus was charged with dimethyl 5-sodium sulfoisophthalate (700 grams, 4.73 equivalents, from DuPont, Wilmington, DE, USA), polyethylene glycol having a molecular weight of 400 (1947 grams, 9,735 equivalents, from Union Carbide Corp., Danbury, CT, USA) and 425 molecular weight polypropylene glycol (1947 grams, 9.184 equivalents, from Arco Chemical Co, Newton Square, PA, USA). The reactor was heated to 345 ° F (174 ° C) and a vacuum was applied to the reactor and maintained for about 1.5 hours. The vacuum was released with nitrogen. Titanium butoxide (3.6 grams) was added and the mixture was heated to 430 ° F. (220 ° C) and kept in this state for 3 hours while collecting methanol. The temperature was then reduced to 345 ° F (174 ° C) and a vacuum was applied to the reaction mixture for 1 hour. The content was subsequently opened 200 ° F (93 ° C) under nitrogen and drained to give a clear, colorless liquid polyol. The measured OH equivalent weight of this polyol is 313 g / mol OH (theoretical OH of 305). The theoretical sulfonate equivalent weight of the polyol mixture is 1879 g polymer / mole sulfonate.

sulfopolyester C

One 5 liter reaction vessel was with 4100 g of polyethylene glycol 600 (13.67 equivalents) and 505.67 g of dimethyl 5-sodium sulfoisophthalate (3.42 equivalents) filled. The materials were placed under full vacuum at 100 ° C for 1 hour long dried. Tetrabutyl titanate (0.08 wt%) was then added, and the reaction mass was heated at 220 ° C until about 85 ° C theoretical methanol were removed. The reaction temperature was at 170 ° C lowered and kept under vacuum for 1 hour, resulting in a clear light yellow material led. The calculated hydroxyl equivalent weight was 428, the calculated sulfonate equivalent weight was 2632.

Examples 1 to 3

The Examples 1 to 3 showed how a variation of the ethanol-water ratio the molecular weight and thus the release adhesion values of the polyurethane dispersion change can.

In A 1 liter reactor was filled with the following components to obtain a 600 gram batch: 120.6 g (1.09 NCO equivalents) isophorone; 147.6 g (0.089 OH equivalents) of KRATON L-2203 hydrogenated Polybutadienediol (OH equivalent weight 1660) from Shell Chemical Co., Houston, TX, USA; 296.4 g (0.291 OH equivalents) TERATHANE 2000 Polytetramethylene oxide diol (OH equivalent weight 1020) from E.I. duPont Co., Wilmington, DE, USA; 6 g (0.05 OH equivalents) SURFYNOL 104 surfactant, a diol from Air Products, Lehigh Valley, PA. USA (OH equivalent weight 113.2); and 24 g (0.110 equivalents) Sulfopolyester diol A as prepared above. This cloudy mixture was stirring under nitrogen to about 80 ° C heated and 0.5 grams of dibutyltin dilaurate catalyst was added. An exothermic reaction occurred to about 90.5 ° C and the reaction became with stirring while continued for about 2.5 hours at 80 ± 5 ° C.

After that were 60 g aliquots (theoretically containing 58.8 milliequivalents residual NCO) of the resulting product in 200 ml glass jars, the 1.48 g (49 milliequivalents Amine) ethylenediamine chain extender in 85.5 g of ethanol solvent and 4.5 g of water solvent (95: 5 ratio, Example 1) or 76.5 g of ethanol and 13.5 g of water (85:15 ratio, Example 2) or 67.5 g of ethanol and 22.5 g of water (75:25 ratio, Example 3). A stir at a moderate speed gave a milky white 40% by weight solids dispersion for all. The resulting dispersions were made to a 0.0015 inch (38 micron) thick Polyester film in a wet coating thickness of about 0.005 inches (127 microns) coated in a 70 ° C forced air oven for 10 minutes dried, whereby clear films were obtained, then overnight at constant temperature (about 22 ° C) and humidity (about 50 ° C) % relative humidity). The samples were with help tested the test method described above. The results are in Table I below.

Table I: Test data for Examples 1 to 3

During the peel tests In Example 1, it was found that the sample was in terms of cohesion failed. As stated, the cohesive strength is a measure of the adhesion of the Thus, Example 1 is not particularly useful embodiment in a cold seal adhesive application. Examples 2 and 3, however showed a low adhesion on glass, but a pretty good self-adhesion, which they use as cold seal adhesives more useful power.

Examples 4 to 8

The Examples 4 to 8 showed how a varying weight ratio of chain extender to the chain terminator, the molecular weight of the polyurethane dispersion impair can.

Corresponding the procedure used in Example 1 was 78.8 g (47.5 Milliequiv. OH) KRATON L-2203 diol, 157.6 g (154.5 milliequiv. OH) TERATHANE 2000 diol, 12.0 g (40 milliequiv. OH) sulfopolyester diol B as prepared above, and 51.5 g (464.3 milliequiv. NCO) Isophorone diisocyanate is filled into a 500 ml reactor and with stirring to about 80 ° C heated under nitrogen. About two (2) drops of dioctyltin dilaurate were added, and an exothermic reaction was detected up to about 87 ° C. After the implementation while about 2 ½ hours the mixture was cooled slightly and 30 g aliquots (with 22.2 milliequivalents of theoretical unreacted NCO) were in 100 ml containers filled, the 45 g of 85:15 ethanol-to-water solutions from Ethylenediamine (EDA chain extender) and 2-amino-2-methyl-1-propanol (AMP, chain terminator) in various conditions contained. These mixtures were mixed with an Omni Macro homogenizer Homogenized by Omni International, Marietta, GA, USA. The coating and The tests were carried out as described in Example 1, with the in Table II results shown below.

Table II: Formulations and Test Data for Examples 4 to 8

During the Tests showed a cohesive failure in Example 8.

Examples 9 and 10

Corresponding of the procedure used in Example 1, 46.7 g (28.1 Milliequiv. OH) KRATON L-2203 diol, 93.3 g (91.5 milliequiv. OH) TERATHANE 2000 diol, 20.0 g (66.7 milliequiv. OH) sulfopolyester diol B as prepared above and 40 g (360.4 milliequiv. NCO) Isophorone diisocyanate is filled into a 500 ml reactor and with stirring to about 80 ° C heated under nitrogen. One drop of dioctyltin dilaurate was added and it became an exothermic reaction to about 82 ° C found. After the implementation while About 2 hours, the mixture was cooled slightly and 30 g aliquots (with 26.1 milliequiv. theoretical unreacted NCO) were placed in 100 ml 45 g of 85:15 ethanol-water solution of 0.81 g or 0.65 g (27 milliequiv.) EDA and 0.48 g (5.4 milliequiv.) Contained AMP. These mixtures were mixed with an Omni Macro homogenizer homogenized.

Comparative Examples A and B

Comparative Examples A and B were prepared according to Examples 9 and 10, respectively, except that the resulting polyurethane dispersion was dispersed in 100% water. Comparative Examples A and B formed cheese-like precipitates and could not be coated. ND means "not determined".

Table III: Formulations and Test Data

Examples 11 to 13

Corresponding of the procedure used in Example 1, 36.8 g (22.2 Milliequiv. OH) KRATON L-2203 diol, 73.6 g (72.2 milliequiv. OH) TERATHANE 2000 diol, 40.0 g (133.3 milliequiv. OH) sulfopolyester diol B and 49.6 g (446.8 milliequivalents NCO) of isophorone diisocyanate filled into a 500 ml reactor and stirring to about 80 ° C heated under nitrogen. One (1) drop of dioctyltin dilaurate was added and it became an exothermic reaction to about 85 ° C found. After the implementation while About 2 hours, the mixture was cooled slightly and 30 g aliquots (32.9 Milliequiv. theoretical unreacted NCO) were placed in 100 ml 45 g of either water or 85:15 ethanol-water solution of 1.00 g (33 milliequiv) of EDA or 0.80 g (26.7 milliequiv.) EDA and 0.60 g (6.7 milliequiv.) Contained AMP. These mixtures were mixed with an Omni Macro homogenizer homogenized. The EDA / AMP / 100 water solution (Example 11) became quite well dispersed and formed a rough / hazy coating. The coating and Testing with the others was done as described in Example 1. The Results are listed in Table IV below, where ND "not determined" means.

Comparative example C

The Comparative Example C became similar as Example 12 is prepared and dispersed in a 100% water-solvent system. Comparative C contained the EDA chain extender but no chain terminator. It made a cheese-like precipitate and could not be coated.

Table IV: Formulations and test data

Examples 14 to 17

157.84 g (95.1 milliequiv. Of OH) of KRATON L-2203 diol, 315.45 g (309.3 mill. Equivalents of OH) of TERATHANE 2000 diol, 24.39 g (81.3 g) were added according to the procedure used in Example 1 Milliequiv., OH) sulfopolyester diol B and 103.4 g (931.5 milliequivalents NCO) of isophorone diisocyanate are charged to a 500 ml reactor and heated with stirring to about 55 ° C under nitrogen. Three (3) drops of dioctyltin dilaurate were added and a slight exotherm was observed. The temperature was raised to about 80 ° C and maintained there for about 2 hours. The mixture was lightly cooled and 90 g aliquots (containing 67.2 milliequivalents of theoretical unreacted NCO) were placed in 500 ml containers containing 135 g of 85:15 ethanol-water solvent system containing EDA and AMP contained in various proportions. These mixtures were homogenized with an Omni Macro Homogenizer. The coating and testing was carried out as described in Example 1, with the results shown in Table V below.

Table V: Formulations and Test Data for Examples 14 to 17

Examples 18 to 21

Of the Following in Example 1, 52.55 g (31.7 milliequiv. OH) KRATON L-2203 diol, 105.09 g (105.1 milliequiv. OH) of polyethylene glycol 2000 Diol from Aldrich Chemical Co., 8 g (36.7 mill. Sulfopolyester diol B and 34.34 g (30.9 meq NCO) isophorone diisocyanate in a 500 ml reactor filled and stirring to about 80 ° C heated under nitrogen. Two (2) drops of dioctyltin dilaurate were added, and it an exothermic reaction was detected up to 86 ° C. The reaction was continued for about 2 hours, after which the mixture became slightly cooled and 30 g aliquots (with 20.4 billion equiv. of theoretical unreacted NCO) were placed in 200 ml containers filled, containing 45g of either water or 85:15 ethanol-water solvent systems, which contained EDA and AMP in different ratios. These Mixtures were homogenized with an Omni Macro Homogenizer, whereby good dispersions were obtained in all cases. The coatings were clear and sticky when removed from the oven, but light cloudy and adhesive-free without adhesion on glass or self-adhesion after conditioning over Night.

Examples 22 to 24

Of the The procedure followed in Example 1 was 78.85 g (47.5 milliequiv. OH) KRATON L-2203 diol, 157.6 g (157.6 milliequiv. OH) of polypropylene glycol 2000 Diol from EM Science, Gibbstown, NJ, USA, 12.2 g (40.7 mill. Sulfopolyester diol B and 52.25 g (470.7 milliequivalents NCO) of isophorone diisocyanate filled into a 500 ml reactor and stirring up to about 80 ° C heated under nitrogen. Two (2) drops of dioctyltin dilaurate were added, and it an exothermic reaction was detected at about 81 ° C. After an implementation while About 2 hours, the mixture was cooled slightly and 30 g aliquots (with 22.4 milliequiv. theoretical unreacted NCO) were placed in 100 ml 45 g of 85:15 ethanol-to-water solvent mixtures contained what EDA and AMP in different proportions contained. These mixtures were homogenized with an Omni Macro homogenizer. The coating and the tests were carried out as described in Example 1, with the results shown in Table VI below.

Table VI: Formulations and Test Data for Examples 22 to 24

Examples 25 to 28

Of the Following the procedure used in Example 1, 25 g (15.1 Milliequiv. OH) KRATON L-2203 diol, 50 g (40.5 milliequiv. OH) TEXOX 5WL-1400, 75/25 Ethylene glycol / propylene glycol of a random copolymer diol having a molecular weight of 2470 from Texaco Chemical, Houston, TX, USA, 4 g (13.3 milliequiv. OH) sulfopolyester diol B and 15.3 g (137.8 milliequivl NCO) isophorone diisocyanate in a 500 ml reactor filled and stirring to about 80 ° C heated under nitrogen. One (1) drop of dioctyltin dilaurate was added and the reaction was continued for about 2 hours. The mixture became light chilled and 20 g aliquots (14.7 billion equiv. of theoretical unreacted NCO) were placed in 100 ml containers containing 30 g of either water or 85:15 ethanol-water solvent mixture containing 0.42 g (14 milliequiv) EDA or 0.37 g (12.3 Milliequiv.) EDA and 0.13 g (1.5 milliequiv.) AMP contained. These mixtures were mixed with an Omni Macro Homogenizer homogenized. The 100% water dispersions (Examples 25 and 26) were very viscous. The coating and tests were done like in Example 1, with those shown in Table VII below Results.

Table VII: Formulations and Test Data for Examples 25 to 28

The Example 26 showed cohesive failure while of the self-removal test. Example 27 showed partial delamination during the Even peel tests. Example 28 showed cohesive failure during both peel tests.

Examples 29 to 31

Following the procedure set forth in Example 1, 26.4 g (15.9 milliequiv. OH) KRATON L-2203 diol, 36.5 g (182.5 milliequiv. OH) of polyethylene glycol diol of molecular weight 400 was obtained from Aldrich Chemical, 4, 8 g (16.0 milliequiv. OH) of sulfopolyester diol B and 31.1 g (280.2 milliequiv. NCO) of isophorone diisocyanate were charged to a 500 ml reactor and heated to about 80 ° C under nitrogen with stirring. One (1) drop of dioctyltin dilaurate was added and an exotherm to about 97 ° C detected. The reaction continued for about 1 hour during which time the viscosity increased.

The Mixture was slightly cooled and 20 g aliquots (with 13.3 milliequivalents of theoretical unreacted NCO) of the thick paste were filled in 100 ml containers containing 30 g of either water or 85:15 ethanol-water solution of 1.86 g (62.0 milliequiv.) EDA or 1.66 g (55.3 milliequiv.) EDA and 0, 58 g (6, 5 milliequiv.) Contained AMP. These mixtures were mixed with an Omni Macro Homogenizer homogenized. The thick paste could not be dispersed in water but could be dispersed with difficulty in ethanol-water and yielded granular coatings. The Coating and the tests were carried out as described in Example 1, with the results shown in Table VIII below.

Table VIII: Formulations and Test Data for Examples 29 to 31

Examples 32 to 37

Of the Following in Example 1 procedure was 40.4 g (24.3 milliequiv. OH) KRATON L-2203 diol, 80.7 g (65.3 milliequiv. OH) TEXOX WL-1400, statistical 75/25 ethylene glycol / propylene glycol copolymer having a molecular weight from 2470 of Texaco Chemical, 6 g (13.3 milliequiv. OH) of sulfopolyester diol C and 23.1 g (208.1 milliequiv. NCO) Isophorone diisocyanate is filled into a 500 ml reactor and with stirring to about 80 ° C heated under nitrogen. One (1) drop of dioctyltin dilaurate was added and it became an exothermic reaction to about 82 ° C found.

To about 2 hours Reaction, the mixture was slightly cooled, and 20 g aliquots (with 14.0 milliequiv. theoretical unreacted NCO) were placed in 100 ml 30 g of either water or 85:15 ethanol-water solution of 0.40 and 0.41 g (13.3 and 13.7 milliequiv.) EDA, respectively, and 13.9 g (13.9 milliequiv.) JEFFAMINE ED2001 polyethylene oxide diamine having a molecular weight of 2000 from Huntsman Corporation, Salt Lake City, UT, USA. TWEEN 40 and STANDAPOL ES2 surfactants were added at 2% by weight of active ingredient to selected Dispersions added. These blends were made with an omni Homogenizer homogenized macro. All samples showed good dispersions. The coating and the tests were carried out as described in Example 1, with the results shown in Table IX below.

Table IX: Formulations and Test Data for Examples 32-37

Examples 38 to 41

Of the Following in Example 1 procedure was 78.8 g (47.5 milliequiv. OH) KRATON L-2203 diol, 157.5 g (154 milliequiv. OH) TERATHANE 2000 diol (T-2000), 12.2g (40.7 milliequiv. OH) sulfopolyester diol B and 51.6 g (464 milliequivalents NCO) of isophorone diisocyanate filled into a 500 ml reactor and stirring to about 60 ° C heated under nitrogen. 3 drops of dioctyltin dilaurate were added and it became an exothermic reaction to about 77 ° C found. The reaction temperature was at 80 ° C raised and maintained there for about 2 hours.

The Mixture was slightly cooled and 50 g aliquots (with 40.0 milliequivalents of theoretical unreacted NCO) of the prepolymer were stirred filled in 200 ml containers, the 60 g of a 85:15 ethanol / water. A mixture of 1.04 g (34.7 milliequiv.) EDA and at 1.3 milliequiv. various amine terminators in 15 g of 85:15 ethanol / water mixture was added in a single serving filled, after the prepolymer was well dispersed. The specific amine terminators that were used were 0.17 g of 2-amino-2-methyl-1-propanol (Example 38), 0.36 g of dodecylamine (Example 39), 0.52 g of octadecylamine (Example 40) and 0.77 g of didodecylamine (Example 41). The coating and the tests were carried out as described in Example 1, with the in Table X results shown below.

Table X: Formulations and Test Data for Examples 38 to 41

Examples 42 to 45

Of the following the procedures used in Examples 38-41 were 77.0 g (76.9 milliequiv. PRIPLAST 3197, a polyester diol of dimer acid of molecular weight from 2000 and Dimerdiol from Uniquema, 154.0 g (151 millivolts OH) TERATHANE 2000 diol, 12.2 g (40.7 milliequiv. OH) sulfopolyester diol B and 56.8 g (511 milliequivalents NCO) of isophorone diisocyanate reacted and dispersed in the same way.

Table XI: Formulations and Test Data for Examples 42 to 45

Examples 46 to 49

Following the procedure followed in Examples 38-41 were 78.8 g (47.5 milliequiv.) Of KRATON L2203-diol, 154.0 g (152 millivolts) of polypropylene glycol having a molecular weight of 2200 (PPG 2200), 12 2.0 g (40.7 milliequiv. OH) of sulfopolyester diol B and 51.6 g (464 milliequiv. NCO) of isopho rondiisocyanat reacted and dispersed in the same way.

Table XII: Formulations and Test Data for Examples 46 to 49

Examples 50 to 55

The for the Examples 38 to 41 and 46 to 49 produced prepolymers (with Terathane 2000 or PPG 2200) were with different Amounts of ethylenediamine and aminomethylpropanol as in Table XIII listed below implemented.

Table XIII: Formulations and Test Data for Examples 50-55

Examples 56 to 59

Of the Following in Example 1 procedure was 25.6 g (20.5 milliequiv. OH) Polybutadienpolyol with an OH equivalent weight of 1250 and a medium functionality from higher as 2, sold under the trade name POLY bd by Elf Atochem, Philadelphia, PA, 51.4 g (51.4 milliequiv. OH) TERATHANE 2000 diol, 4.2 g (13.4 milliequiv. OH) sulfopolyester diol B and 18.9 g (170 milliequivalents NCO) of isophorone diisocyanate filled in a 250 ml reactor and stirring to about 60 ° C heated under nitrogen. Two (2) drops of dioctyltin dilaurate were added and it became an exothermic reaction to about 71 ° C found. The reaction temperature was at 80 ° C elevated and maintained there for about 2 hours.

The Mixture was slightly cooled and 20 g aliquots (16.9 milliequivalents theoretical unreacted NCO) of the prepolymer were stirred filled in 100 ml containers, the 30 g of a 85:15 ethanol / water mixture containing varying amounts of EDA and AMP. The coating and the tests were carried out as described in Example 1, with the results shown in the table below.

Table XIV: Formulations and Test Data for Examples 56 to 59

Examples 60 to 79

Of the Following in Example 1, KRATON L-2203 diol and TERATHANE 2000 diol in different proportions with isophorone diisocyanate (IPDI) and selected stabilizers including cationic VARIQUAT K1215 diol from Witco, polyethylene glycol with a molecular weight of 600, dimethylolpropanoic acid (DMPA), Sulfopolyester diol B, or without an added stabilizer, implemented. The prepolymers were in ethanol-water, the EDA chain extender and AMP chain terminator contained as specified below dispersed. The coating and the tests were carried out as described in Example 1, with the same results shown in Table XV.

Cosmetic Example 1

A body lotion suitable for use as a water-repellent sunscreen or In anti-segregant with added active ingredients was prepared. An oil-in-water emulsion was prepared using the specific components and weight percentages listed for Phase A and Phase B listed in Table XVI. Phase A and Phase B were heated to 70 ° C with continuous stirring in separate containers. Phase B was added to Phase A and homogenized using a high shear mixer. Cooling to room temperature with gentle agitation gives a cream of moderate viscosity.

Table XVI. Oil-in-water emulsion for body lotion

Cosmetic Example 2:

An oil-in-water emulsion for mascara was determined using the specific ones listed in Table XVII Components and amounts in wt .-% for the phase A and phase B produced. Phase A and Phase B were heated to 90 ° C with continuous stirring separate containers heated. Phase B was added to Phase A and with the help of a high shear mixer homogenized. After cooling sees the resulting paste a flake, dirt and water resistant mascara in front.

Table XVII. Oil-in-water emulsion for mascara

Cosmetic Example 3:

A conditioning shampoo was made by charging 35.7 wt% ammonium lauryl sulfate (28% solids), 24 wt% ammonium laureth-2 sulfate (25% solids), 3 wt% ethylene glycol distearate, 1 wt% cocamide MEA and 31.2 wt% deionized water in a container. The resulting mixture was heated to 80 ° C with stirring, and a mixture containing 5% by weight of the dispersion of Example 16 was added in 5% by weight of C ₁₂ to C ₁₅ alkyl benzoate. After cooling, the resulting bead-like liquid provides a shampoo with good combability after rinsing and rapid drying.

Cosmetic Example 4.

One Nail clearcoat was prepared as follows: About 20 parts of an ethanol solution with 20% solids of an acrylate-grafted silicone copolymer, available from 3M Corporation, St. Paul, MN, under the trade designation VS 80 Silicones Plus copolymer, was mixed with 1 part of the dispersion solution of Example 16 combined. This resulted in a quick-drying nail varnish provided with good chip resistance and gloss.

Cosmetic Example 5:

One Shampoo was through filling of 36% by weight of ammonium lauryl sulfate (28% solids), 24% by weight Ammonium laureth-2-sulfate (25% solids), 3% by weight ethylene glycol distearate, 1 wt .-% cocamide MEA and 6 wt .-% deionized water in one container produced. The resulting mixture was heated to 80 ° C with stirring Formation of a pearly liquid. After cooling was 30% by weight of the 40% solids dispersion of Example 36 added, to provide a shampoo that is a foamy, slippery feel when used with 0.5 milliliters on a 2 g hair sample and good wet combability after rinsing and quick drying leads.

Cosmetic Example 6:

A shampoo was prepared by charging 50% by weight of ammonium lauryl sulfate (28% solids), 11% by weight of disodium cocoamphodiacetate (50% solids), and 9% by weight of deionized water to a container. The resulting mixture was heated to 80 ° C with stirring to give a clear liquid. After cooling, 30% by weight of the 40% solids dispersion of Example 36 was added to provide a milky shampoo which has a foamy, slippery feel, when used at 0.5 milliliters on a 2 gram hair sample and results in good wet combability after rinsing and quick drying.

Cosmetic Example 7:

One Shampoo was through filling of 39% by weight ammonium lauryl sulfate (28% solids), 11% by weight Cocamidopropylbetaine (35% solids) and 20% by weight deionized Water produced in a container. The resulting mixture was heated to 80 ° C with stirring to give a clear Liquid. After cooling was 30% by weight of the 40% solids dispersion of Example 36 added, to provide a shampoo that is a foamy, slippery feel when used with 0.5 milliliters on a 2 g hair sample and good wet combability after rinsing and Quick drying leads.

Cosmetic Examples 8 to 19th

Under Using the same ingredients and procedure as in the cosmetic example 7, the amounts of the polymer dispersion and of water varies, whereby polymer contents in the range of 0.5 to 11 wt .-% were obtained, as shown in the table below.

All cited herein References are by reference to each in their entirety including.

Claims (26)

Polyurethane dispersion in a mixture is stable from alcohol and water, the dispersion being the reaction product of the following includes: (a) at least one isocyanate-terminated Polyurethane prepolymer comprising the reaction product of (i) at least one polyactive A hydrogen compound which is insoluble in the alcohol, wherein the polyactive hydrogen compound an alkyl, aryl or aralkyl structure, which may be by N, O or S or combinations thereof in or on the chain is substituted; (ii) at least one polyisocyanate and (iii) at least one polyactive hydrogen compound in the mixture soluble in alcohol and water is (b) at least one polyfunctional chain extender; and (c) at least one chain terminator. Polyurethane dispersion according to claim 1, wherein the equivalent ratio of the chain extender to the prepolymer isocyanate 0.60: 1 to 1: 1.2. A polyurethane dispersion according to claim 1, wherein the chain terminator is monofunctional. Dispersion according to claim 1, wherein component (a) (i) is selected from the group consisting of those from oligomeric polyols and oligomeric polyamines with on average about 1.6 to 4 hydroxyl and / or amino groups. Dispersion according to claim 1, wherein component (a) (i) is selected from the group consisting of polybutadiene polyols, polyisoprene polyols, hydrogenated polybutadiene polyols, hydrogenated polyisoprene polyols, polyester polyols of dimer diacids, polyester polyols consists of dimer diols, dimer diols and combinations thereof. Dispersion according to claim 1, comprising at least 5 wt .-% of component (a) (i), based on the total weight of components a (i), a (ii) and a (iii). Dispersion according to claim 1, wherein the polyisocyanate is selected from the group consisting of dicyclohexylmethane-4,4'-diisocyanate; 3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane, tetramethylene; 1,3-bis (isocyanatomethyl) cyclonexan; 1,3-bis (1-isocyanato-1-methylethyl) benzene; Diphenylmethane-4,4'-diisocyanate; 4,4 ', 4' '- Triisocyanatotriphenylmethan; polymethylene, toluene diisocyanate; hexamethylene diisocyanate; dodecamethylene; m- and p-xylenediisocyanate and combinations thereof. Dispersion according to claim 1, wherein component (a) (iii) is selected from the group those from (i) a compound containing an ionic group, (ii) a compound containing a radical capable of forming an ionic Group is capable of (iii) a compound which is a polyester, Polyether or polycarbonate group in a proportion of 5 or less Carbon atoms for contains each oxygen atom; and (iv) mixtures thereof. A dispersion according to claim 8 wherein component (a) (iii) is a cationic compound having the structure: RN ⁺ (R ₂ ) [(CH ₂ CH ₂ O) _n H] ₂ X wherein R is C ₁ to C ₁₈ alkyl or C ₆ to C ₁₈ aryl or aralkyl optionally substituted in and / or on the chain by N, O or S or combinations thereof; R _{2 is} hydrogen or C ₁ to C ₁₈ alkyl; n is an integer from 1 to 200; and X is halogen, sulfate, methosulfate, ethosulfate, acetate, carbonate or phosphate. A dispersion according to claim 8, wherein component (a) (iii) is a compound of the following structure.

wherein each R _{1 is} independently a divalent aliphatic group having an average molecular weight of 200 to 600, comprising ether or ester functional groups selected from the group consisting of -CH ₂ -CH ₂ - (OCH ₂ -CH ₂ -) _n -, -C (CH ₃ ) H-CH ₂ - (OC (CH ₃ ) H-CH ₂ -) _n -, - (CH ₂ ) ₄ - (O (CH ₂ ) ₄ ) _n -, - (CH ₂ ) _m -CO - [- O- (CH ₂ ) _m -CO-] _n groups; and mixtures thereof; wherein m is an integer of 2 to 5 and n is an integer of 2 to 15; and M is selected from the group consisting of Na, H, K, Li, ammonium, methylammonium, butylammoni , diethylammonium, triethylammonium, tetraethylammonium and benzyltrimethylammonium cation. Dispersion according to claim 1, wherein the chain extender chosen is from the group consisting of water; ethylenediamine; 1,6-diaminohexane; piperazine; Tris (2-aminoethyl) amine; Amine-terminated polyethers; adipic; oxalic acid; Ethylene glycol; 1,4-butanediol; 1,8-octane; 1,2-ethanedithiol; 1,4-butanedithiol; 2,2'-oxytris (ethane thiol); and di- and tri-mercaptopropionate esters of poly (oxyethylene) diols and triols. Dispersion according to claim 1, wherein the polyurethane dispersion has an ionic content of about 1000 to 15 000 g prepolymer per equivalent ionic group possesses. Dispersion according to claim 1, wherein the reaction product has a weight average molecular weight of has about 5,000 to 50,000. Dispersion according to claim 1, wherein the dispersion further comprises a lower alcohol. Dispersion according to claim 14, wherein the lower alcohol is selected from the group consisting of ethanol, n-propanol, 2-propanol and combinations thereof. Dispersion according to claim 14, wherein the composition is at least 20% by weight of the lower alcohol includes, based on the total weight of the composition. A cold seal adhesive comprising the dispersion of claim 1. Adhesive according to claim 17, which shows self-adhesive properties when it becomes one Film coated with a thickness of about 0.025 millimeters and is dried. Adhesive according to claim 17 with a value of self-adhesion of more than 5 Newton per decimeter. Adhesive according to claim 17 with a value of adhesion on glass of less than 10 Newton per decimeter. Product comprising the dispersion according to claim 1, wherein the product is selected from the group consisting of self-adhesive envelopes, bundle tapes, heat-sensitive Products, containers, Text binders, medical products, medical packaging materials Products and diaper closures consists. saturant in a cohesive elastomeric bandage comprising the dispersion according to claim 1. Cosmetic application comprising the dispersion according to claim 1, wherein the cosmetic application is selected from the group, made of mascara, foundation, rouge, face powder, eyeliner, eye shadow, Lipstick, insect repellent, nail varnish, moisturizer, Skin cream, body lotion and sunscreen exists. A hair care composition comprising the dispersion according to claim 1, wherein the hair care composition is selected from the group consisting of from shampoos, hair conditioners, Hair sprays, foams and Gels, and wherein the hair care composition is non-reconstitutable Hairstyling composition is. Dispersion according to claim 1, further comprising an additive selected from the group consisting of defoamers, flow and leveling agents, rheology modifiers, photostabilizers and combinations thereof. A polyurethane dispersion which is stable in a mixture of alcohol and water, the dispersion comprising the reaction product of: (a) an isocyanate-terminated polyurethane prepolymer comprising the reaction product of (i) about 20 to 30 parts by weight hydrogenated polybutadiene diol , (ii) about 15 to 30 parts by weight of isophorone diisocyanate, and (iii) about 0 to 10 parts by weight sulfonated polyester diol and about 25 to 75 parts by weight polytetramethylene oxide diol; (b) about 0.05 to 5 parts by weight of ethylenediamine; and (c) about 0 to 5 parts by weight of 2-amino-2-methyl-1-propanol.